Flameproof finishing of cellulose, fibers and articles containing them

ABSTRACT

The present invention is directed to a method for the permanent flameproof finishing of cellulose fibers and articles containing them. The flameproof finishing takes place using a 4,6-dichloro-1,3,5-triazine-2-yl amine compounds.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] The present application claims priority under 35 U.S.C. §119 toGerman application 100 38 100.6, filed on Aug. 4, 2000, the text ofwhich is hereby incorporated by reference.

FIELD OF THE INVENTION

[0002] The invention is directed to a method for the permanentflameproof finishing of cellulose fibers by treating the fibers with acyanuric chloride derivative in aqueous phase. The invention alsoincludes the finished cellulose fibers and articles in which they areused such as yarns, fleeces and textile fabrics.

BACKGROUND

[0003] Various methods are known which can be used for the permanent,i.e., wash-resistant, and non-permanent finishing of cellulose fibers,especially cotton fibers. Flameproof textiles made using such finishedfibers are used in proactive clothing, children's clothing, curtains andupholstery. Flameproof finishes often utilize inorganic salts such asammonium hydrogen phosphate, ammonium sulfate, borax and boric acid,that can optionally be combined with organic nitrogenous bases. Inparticular, phosphorus flameproofing agents and phosphorus-nitrogenflameproofing agents are used for permanent flameproof finishing. Thesemay be either adsorbed onto fibers or applied as a monomer orpre-condensate and hardened in the form of a polymer on the fiber. Forexample, pre-condensates of tetrakishydroxymethylphosphonium hydroxideand urea may be applied to the fiber, followed by a treatment withammonia and then with hydrogen peroxide (Melliand Textilberichte3:219-224 (1990)). This and similar methods are expensive and result ina product that is relatively stiff. A good flameproof finishing can alsobe achieved in the case of cotton using dialkylphosphono-carboxylic acidamides and melamine resins. However, this results in a substantial lossof tear strength.

[0004] Various ammino-1,3,5-triazines have also become known for theiruse in the permanent finishing of cotton and are bound via methylolgroups to cellulose fibers. According to Schanz (Textile ResearchJournal, 418-422 (June 1977))tetramethylol-2,4-diamino-6-(3,3,3-tribromo-1-propyl)-1,3,5-triazinefunctions as a flameproofing agent. This agent is applied in the form ofan aqueous dimethylformamide solution and polymerizes at elevatedtemperature on the fiber. A significant disadvantage of this method, theuse of dimethylformamide, is avoided in the method of Moreau et al.(American Dyestuff Reporter, 7-38 May (1970)) by using2-amino-4,6-bis-diethoxy-phosphinyl-1,3,5-triazine or2,4-diamino-6-diethoxy-phosphinyl-1,3,5-triazine in aqueous formaldehydesolution. Sello et al. (Textilveredelung 5:391-399 (1970)) teach otherflameproofmg agents based on 1,3,5-triazine compounds containingN-methylolamino-and phosphonic acid ester groupings. All these methodsdescribe compounds that are bound to cellulose fibers by N-methylolgroups. Aside from a loss of tear strength, the use of formaldehyde or asource of formaldehyde is a disadvantage.

[0005] It is known that cellulose can be reacted with cyanuric chlorideor with 2-amino-4,6-dichloro-1,3,5-triazine in the presence of a baseand that the reaction product can be subsequently reacted with a dye(U.S. Pat. No. 1,886,480; U.S. Pat. No. 2,025,660; Rauh, MelliandTextilberichte 10:1195-1200 (1971)). However, these references do notsuggest that cotton can be flameproofed by reaction withdichlorotriazinyl amines or similar compounds. Dichlorotriazinyl aminocompounds containing sulfonic acid groups (see e.g., WO 97/49856) aswell as quaternary compounds based on bistriazinyl amines with onechlorine atom each in the triazine ring (see e.g., Evans, JSDC100:304-314 (October 1984)) can be used as auxiliary textile agents formodifying cellulose in order to improve its dyeing affinity.

[0006] An important prerequisite for the successful use of reactivetriazine derivatives in flameproof finishing, is to achieve a highdegree of substitution during the reaction of the triazine derivativewith the cellulosic material. With respect to the dyeing qualities ofthe material, experience has shown that an even slight modification ofthe cellulose material with the triazine derivatives cited has a greatinfluence. However, in order to achieve a flameproofing effect orself-extinguishing qualities, it is necessary to apply a large amount ofcompound and this tends to make procedures expensive.

[0007] Ideally a method for flameproof finishing should allow a highdegree of substitution of cellulosic material under economicallyacceptable conditions and avoid the use of formaldehyde or substancesthat release formaldehyde. In addition, it should feasible to carry outthe method with the customary devices of a textile operation and, inparticular, the high expense for an ammonia vaporization plant should beavoided. Finally, the method should make it possible to achieve thepermanent flameproofing or self-extinguishing of cellulose fibers withan LOI value (limiting oxygen index according to ASTM D2863-77) of 24 or27 and higher without appreciably influencing the tear strength.

SUMMARY OF THE INVENTION

[0008] The present invention is concerned with a method for flameprooffinishing that does not have the disadvantages of the previously knownmethods. It involves exposing cellulose fibers or the articlescontaining them to alkaline conditions to swell fibers, and thentreating them with a cyanuric chloride derivative in aqueous-alkalinephase. The cyanic chloride derivative is a4,6-dichloro-1,3,5-triazine-2-yl amine of formula I or II:

[0009] in which R¹ and R² are the same or different and are selectedfrom the group consisting of: H; (C₁-C₆) alkyl; benzyl; phenyl; ω-amino(C₂-C₆) alkyl; ω-hydroxy (C₂-C₆) alkyl; (CH₂)_(m)SO₂—OH or—(CH₂)_(m)—COOH, in which m is 1 or 2, as well as their amides;(CH₂)_(n)—P(O)(OR′)₂ in which n=1, 2 or 3 and R′═H, CH₃ or C₂H₅; o-, m-or p-C₆H₄SO₂NH₂; and o-, m- or p-C₆H₄—N(CH₃)₃⊕; or R¹ and R² togetherform an ethylene trimethylene- or bismethylene imino group; R³ informula II is selected from the group consisting of: para- ormeta-phenylene; 1,4-, 1,3- or 2,6-naphthylene; (C₂-C₆) alkylene;—C₂H₄—NH—C₂H₄—; C₂H₄—NH—C₂H₄—NH—C₂H₄—; C₂H₄—O—C₂H₄—; andC₆H₄—NHCONH—C₆H₄—; and R⁴ is selected from the group consisting of: H;(C₁-C₃) alkyl; aminoethyl; and aminopropyl; or both R⁴ groups togetherform ethylene or propylene.

[0010] The method in accordance with the invention achieves permanentflameproof finishing of cellulose fibers and articles containing themsuch as yarns, fleeces and sheet articles, e.g., fabric, knit goods andknitwear. The finished fibers contain amino-s-triazine compounds boundto glucose units of the cellulose via ether bridges. The permanentlyfinished cellulose comprises a structure in accordance with formula IIIor IV:

[0011] In formulas III and IV the groups R¹, R², R³ and R⁴ have the samedefinitions as for formulas I and II; R⁵ stands for Cl, OH, Ocell, OR⁶or NHR⁶, with R⁶ standing for a

[0012] dye group; “cell” stands for an anhydroglucose unit of celluloseand q for the degree of substitution. Q can assume any value in therange of greater than 0 to 3. Although, in the first stage of themethod, R⁵ is still generally chlorine, it can be converted by furtherreaction with a glucose unit of cellulose into Ocell or by a reactionwith a dye into OR⁶ or NHR⁶.

[0013] A permanent flameproof finishing results from the chemicalreaction of the derivative with cellulose. This type of finishing may becontrasted with previous flameproof finishings in which polymers areembedded in the fiber and cross-linked. In the present method, covalentlinkage of the active substances to the fiber creates no appreciableloss in tear strength or in the gripping qualities of sheet materials.

[0014] The concept “flameproof finishing” is to be understood to meanthat the finished cellulose fiber and articles containing it are lessreadily combustible and/or extinguish themselves more rapidly after theremoval of the source of ignition than is the case for non-finishedfiber or articles containing it. A measure for flameproof finishing isthe so-called LOI value according to ASTM D2863-77. The LOI indicatesthe limit value of the volumetric fraction of oxygen in anoxygen/nitrogen atmosphere in which a textile fabric is still burningfrom the top downward. The higher the LOI value the better theflameproof finishing. Above a LOI of 24 one speaks of flame-retardingqualities and at values of 27 and higher of self-extinguishingqualities.

[0015] The quality of the flameproof finishing is a function of thecomponents with active flameproofing and amount used relative to thefiber weight. As is apparent from the state of the art nitrogenouscompounds and phosphorous-containing compounds act in a flameproofingmanner. The cyanuric chloride derivatives used in accordance with theinvention make it possible to adjust the nitrogen content of thecellulose to values that bring about a flameproofing orself-extinguishing quality. Self-extinguishing qualities are to beexpected, e.g., in cotton fibers or a cotton article at an N content ofapproximately 3%. Self-extinguishing qualities can be expected at a Pcontent of approximately 2.2% when using a phosphorus-containingflameproofing agent. The two elements can be substituted; a synergisticeffect is frequently achieved by the combination of both elements.

[0016] The cyanuric chloride derivatives in accordance with theinvention are reactively linked with the OH groups of the cellulose.Theoretically, three hydroxyl groups per anhydroglucose unit areavailable for reaction, so that a maximum value of 3 for the degree ofsubstitution results. This high degree of substitution is possible inthe case of cellulose either only in a homogeneous reaction or, in thecase of a heterogeneous reaction, only if cellulose fibers have beenpre-swollen. Moreover, complete substitution can usually only beachieved for a very few, usually non-polar, substituents (e.g.,trimethylcellulose, trimethylsilylcellulose). In the case of stericallyexacting substituents, such as triazine derivatives, and that areapplied in aqueous solution, usually far lesser degrees of substitutionare obtained, even under drastic reaction conditions. Thus, it can becalculated, e.g., that given a coloration of average depth with reactivedyes (e.g., dichloro- or monochloro- reactive anchor dye) a substitutiontakes place only on every twentieth to fiftieth anhydroglucose unit.

[0017] In order to obtain higher degrees of substitution, which are aprerequisite for a flameproof finishing (see nitrogen content), thecyanuric chloride derivatives used in accordance with the invention areapplied after a preceding swelling of the fibrous material in aqueousalkali. According to a preferred embodiment, at least 0.05 mole cyanuricchloride derivative according to formula I or at least 0.025 mole of thederivative according to formula II is used per glucose unit of thecellulose. The cyanuric chloride derivative is preferably used in anamount such that the degree of substitution, q, is in the range ofapproximately 0.1 to 1. Depending on the structure of the cyanuricchloride derivative, a different nitrogen content of the finishedcellulose will result. The dichlorotriazinyl derivative according toformula I or II is advantageously used in such an amount that thefinished cellulose has a nitrogen content of at least 2% by wt., andpreferably 3 to 10% by wt. Cyanuric chloride derivatives in accordancewith the invention are advantageously used in an amount of 10 to 100% bywt., and preferably 20 to 80% by wt.

[0018] FIG. 1 shows the dependency of the LOI value on the nitrogencontent of the cotton article that has undergone flameproof finishing.The finishing took place using 2-ammino-4,6-dichlorotriazine. The figureincludes measurements derived from examples 1 and 2.

[0019] It is possible to treat cellulose fibers with aphosphorus-containing flameproofmg agent before, during, or afterfinishing in accordance with the invention. Such treatment will resultin the phosphorus-containing flameproofing agent encasing the cellulosefibers in the form of a polycondensate or, preferably, thephosphorus-containing agent will react with the fibers. Thephosphorus-containing, or other, flameproofing agent is used in anamount such that the finished cellulose has a phosphorus content of atleast 1% by wt., and preferably at least 2% by wt.

[0020] The cellulose fibers that are to be permanently finished can benative fibers, especially cotton fibers, solvent-spun cellulose fiberssuch as, e.g., lyocell, or regenerated fibers such as viscose fibers orcarbamate fibers. The cellulose fibers can be used in the form of aflock, fleece, fabric, knit goods or knitwear or other sheet article.Yarns consisting essentially of cellulose fibers can also be used. Yarnsand sheet articles that also contain fibers other than cellulose shouldgenerally only be used in the method, if the other fibers can enter intoa chemical bond with the cyanuric chloride derivative in a mannersimilar to that of a cellulose fiber. Naturally, cellulose fibersfinished in accordance with the invention can be combined with otherfibers that are, optionally, flameproof finished in a completelydifferent manner, and converted into yarn and textile articles.

[0021] In order to carry out the method of the invention, the cellulosefiber or an article containing it is customarily reacted in aqueous,alkaline phase with the cyanuric chloride derivative. When cotton orcotton articles are used, the treatment can advantageously be carriedout in such a manner that at first a treatment with sodium hydroxidesolution takes place, during which the cotton swells. After beingsqueezed to a residual moisture of below 100% the cellulose alkalized inthis manner is brought in contact with an aqueous solution or asuspension of a cyanuric chloride derivative of formula I or II. Thiscontacting can take place in the presence or the absence of customarytextile agents such dispersing agents. The treatment can be carried outin apparatuses familiar to those skilled in the art of textiletreatments, e.g., in a dyeing apparatus. Treatment can be carried out atroom temperature, but, preferably, a moderately elevated temperature isused, preferably in the range of 30 to 80° C., and more at 50 to 70° C.Treatment time may vary from a few minutes to a few hours.

[0022] The required amount of cyanuric chloride derivative can beapplied onto the fiber in one step or in several steps. After the actualtreatment, non-reactively bound cyanuric chloride derivative and excessalkali are washed away with water, preferably boiling water. During thispost-treatment, chlorine atoms still present on the cyanuric chlorideare replaced by hydroxyl groups. After the treatment of the cellulosefiber with the cyanuric chloride derivative, the resulting product maybe dyed with a customary dye for cellulose before or afterpost-treatment. In so far as the finished cellulose still has reactivechlorine atoms on the cyanuric chloride before the dyeing process, thedye can be reactively bound to them. As an alternative, the flameprooffinishing of the invention can also be carried out on a cellulose fiberthat is entirely or partially dyed or on an article containing it.

[0023] The treatment of cellulose with a cyanuric chloride derivative,as well as its post-treatment or fixing are customary process steps inthe textile art. Procedures and techniques that are apparent from theexisting art are part of the invention.

[0024] Among the cyanuric chloride derivatives that are to be used inaccordance with the invention and that are a dichlorotriazinyl aminesaccording to formula I or bis(dichlorotriazinyl)diamines according toformula II, the following compounds are especially preferred:2-amino-4,6-dichlorotriazine; 2-aminoethylamino-2,4-dichloro-triazine;2-(p-benzenesulfonamide-amino)-4,6-dichlorotriazine; a salt, especiallya halogenide of2-(p-trimethylammonium-benzene-amino)-4,6-dichlorotriazine;bis-N,N′-4,6-dichloro-triazine-2-yl)-p-phenylene diamine; bis-N,N′-4,6-dichlorotriazine-2-yl)-(C₂ to C₄) alkene diamine; andbis-(4,6-dichlorotriazine-2-yl)-aminoethylphosphonate.

[0025] If a phosphorus-containing agent is used for flameproof finishingin addition to a cyanuric chloride derivative as described above, thiscan take the form of a single agent, i.e., a phosphorus-containingtriazine derivative in accordance with the invention. However, it isalso possible to apply a phosphorus-containing flameproofing agent ontothe fiber by further treatment, e.g., by treating the fiber with aflameproofing agent selected from dialkylphosphonocarboxylic acid amidesand their methylol compounds, phosphonates and/ortetrakishydroxymethylphosphonium salts.

[0026] Preferred cellulose fibers produced in accordance with theinvention or articles containing them comprise the groups R¹, R², R³ andR⁴ in the structural elements according to formula III or IV. Rspreferably stands for OH and/or Ocell. A cross-linking of the cellulosecan occur to a certain extent by using the dichlorotriazinyl compoundsor bis(dichlorotriazinyl) compounds of the invention. A crease-resistantfinish is achieved at the same time as the flameproof finish as a resultof this cross linking. In a manner similar to that described for theflameproof finishing, the creaseproof finishing is a function of theamount and reactivity of the dichlorotriazine compound used and, inaddition, of conditions such as temperature, pH and concentration usedduring treatment and the post-treatment.

[0027] Advantages of the method include the ability to carry outtreatment in a simple manner, the ready accessibility of the cyanuricchloride derivatives suitable for use as flameproofmg agents and theirhigh content of the nitrogen necessary for flameproofing. The degree offlameproofing can be adjusted based upon the amount of cyanuric chloridederivative used and, in addition, based upon the usephosphorus-containing flameproofing agents. A LOI value of above 25 canbe easily achieved. Another advantage is that tear strength is onlyminimally reduced while, at the same time, crease resistance increases.The use of a cationic cyanuric chloride derivative makes it possible toobtain a higher degree of exhaustion in subsequent dying steps. Thus,more intensive dying can be achieved.

[0028] The following non-limiting examples illustrate the invention.

EXAMPLES Example 1

[0029] A cotton fabric strip (16 g, scoured, bleached, 136 g/m2) isswollen for 3 min. in 700 ml sodium hydroxide solution (300 g/l). Thematerial is subsequently squeezed out to a residual moisture of 80%. Thestrip is placed loosely wound into a bucket of high-grade steel andcompounded with a suspension of aminodichlorotriazine (4 g, 165 g/mol,0.024 mol) in 50 ml water containing 0.2 g of a dispersing agent(naphthalene sulfonate). It is heated in a laboratory dyeing apparatus(Polymat of the Ahiba company in Switzerland) to 65° C. and agitated 1hour at this temperature. Non-reacted aminodichlorotriazine and excesssodium hydroxide solution are then washed out with boiling water.

[0030] A nitrogen content of 3% is obtained. The LOI of the finishedfabric is 21.6, which may be contrasted with that of the untreatedcotton fabric, 17. The tear strength, determined using a test accordingto DIN 53859 is 7.3 N (F_(agent)) for the untreated fabric and 7.2 N forthe fabric finished with aminodichlorotriazine. Thus, it decreases onlyto a negligible extent. The angle of wet crease recovery increases bythe treatment from 66° to 110° (complete recovery 180°).

Example 2

[0031] A cotton fabric strip (16 g, scoured, bleached, 136 g/m²) isswollen for 3 min. in 700 ml sodium hydroxide solution (300 g/l). Thematerial is subsequently squeezed out to a residual moisture of 80%. Thestrip is impregnated with a suspension of aminodichlorotriazine (4 g,165 g/mol, 0.024 mol) in 50 ml water containing 0.2 g of a dispersingagent (naphthalene sulfonate). The strip is subsequently wound on aroller, packed airtight and agitated for 24 hours (cold pad-batch dyeingprocess). Then, non-reacted aminodichlorotriazine and excess sodiumhydroxide solution are washed out with boiling water.

[0032] A nitrogen content of 1.6% is obtained. The LOI of the fabric is19.1.

Example 3

[0033] A cotton fabric strip (16 g, scoured, bleached, 136 g/m²) isswollen for 3 min. in 700 ml sodium hydroxide solution (300 g/l). Thematerial is subsequently squeezed out to a residual moisture of 80%.2-(p-benzene sulfonamide-amino)-4,6-dichlorotriazine (8 g) is dissolvedunder addition of sodium carbonate in 50 ml water. The caustified cottonstrip is placed with this solution into a high-grade steel bucket. Thepreparation is heated in a laboratory dyeing apparatus to 65° C. andagitated one hour at this temperature. Then, non-reacted 2-(p-benzenesulfonamide-amino)-4,6-dichlorotriazine and excess sodium hydroxidesolution are washed out with boiling water.

[0034] A nitrogen content of 2.4% is obtained. The LOI of the fabric is22.

Example 4

[0035] A cotton fabric strip (16 g, scoured, bleached, 136 g/m²) isswollen for 3 min. in 700 ml sodium hydroxide solution (300 g/l). Thematerial is subsequently squeezed out to a residual moisture of 80%.Bis-N,N′-(4,6-dichloro-2-amino-triazinyl)-p-phenylene diamine (4 g, 404g/mol, 0.01 mol) is suspended in 50 ml water with the addition of 0.2 gof a dispersing agent (Avolan IS). The caustified cotton strip iscompounded with this solution in a high-grade steel bucket. Thepreparation is heated to 65° C. in a laboratory dyeing apparatus andagitated one hour at this temperature. Then, non-reactedbis-N,N′-(4,6-dichloro-2-amino-triazinyl)-p-phenylene diamine and excesssodium hydroxide solution are washed out with boiling water.

[0036] A nitrogen content of 4.6% is obtained. The LOI of the fabric is23.

Example 5

[0037] A cotton fabric strip (16 g, scoured, bleached, 136 g/m²) isswollen for 3 min. in 700 ml sodium hydroxide solution (300 g/l). Thematerial is subsequently wrung out to a residual moisture of 80%.2,4-dichloro-6-(m-trimethylammonium-benzeneamino)-triazine iodide (8 g,426 g/mol, 0.019 mol) is dissolved in 50 ml water. The caustified cottonstrip is compounded with this solution in a high-grade steel bucket. Thematter is heated to 65° C. in the laboratory dyeing apparatus andagitated for one hour at this temperature. Non-reacted2,4-dichloro-6-(m-trimethylammonium-benzeneamino)-triazine iodide andexcess sodium hydroxide solution are then washed out with boiling water.

[0038] A nitrogen content of 1.3% is obtained. The LOI of the fabric is18.5.

Example 6

[0039] A cotton fabric strip treated with aminodichlorotriazine (8 g,nitrogen content 2.2%) is impregnated with a solution of 13 g sodiumdihydrogen phosphate in 100 ml water. It is wrung out to a residualmoisture of 80% and the fabric strip dried at 60° C.

[0040] An additional coating weight of 9.8% is obtained. The LOI of thefabric rises from 20 to 27.2.

Example 7

[0041] A cotton fabric strip treated with aminodichlorotriazine (8 g,nitrogen content 3%) is impregnated with a mixture of 60 g of adialkylphosphono carboxylic acid amide solution (Aflammnit KWB,Thor-Chemie), 3.5 g phosphoric acid and 40 ml water. The strip is wrungout to a residual moisture of 80% and dried 1 min. at 100° C. in alaboratory dryer (Mathis A G, Switzerland). The strip is then fixed inthe same device at 150° C. for 5 min. The fabric strip is washed hot andthen several times cold.

[0042] A phosphorus content of 2.5% and a LOI of 32 is obtained. Thewash resistance of the finish is just as good as in the case of anuntreated fabric in which the finishing bath contains a cross-linkingagent.

Example 8

[0043] A cotton fabric strip treated with aminodichlorotriazine (8 g,nitrogen content 3%) is impregnated with a solution of 16 g ammoniummonomethylphosphite and 8 g urea in 24 ml water. The strip is wrung outto a residual moisture of 80% and dried 1 min. in a laboratory dryer at100° C. The strip is then fixed in the same device at 150° C. for 5 min.The fabric strip is washed hot and cold.

[0044] A phosphorus content of 3% and a LOI of 38 is obtained. Thefinishing lasts through five 60° C. washes.

Example 9

[0045] A cotton fabric strip treated with aminodichlorotriazine (1.8 g,nitrogen content 2.2%) is dyed with a cationic dye (Basic Blue 4; 4%dyeing at a liquor ratio of 1:50) with the addition of 1.35 ml 60%acetic acid, 1.8 g sodium acetate and 9 g sodium sulfate at 85° C. for45 min. The strip is then washed several times.

[0046] The degree of exhaustion of the dyeing rises from 30 % (untreatedfabric) to 41 % (fabric pretreated with AdCT). Distinctly more dye isalso fixed on the fabric; the K/S value rises from 2.1 to 11.2.

Example 10

[0047] A cotton fabric strip treated with2,4-dichloro-6-(m-trimethylammonium-benzeneamino)-triazine iodide (1.8g, nitrogen content 1.7%) is dyed with a reactive dye (Reactive Black 5;5% dyeing at a liquor ratio of 1:20) with the addition of 50 g/l sodiumsulfate, 15 g/l sodium carbonate and 1.5 ml/l sodium hydroxide solution(32.5%) at 60° C. for 1 hour. The strip is then washed hot and coldseveral times.

[0048] The degree of exhaustion of the dyeing rises from 58% (untreatedfabric) to 65% (pretreated fabric). Distinctly more dye is fixed on thefabric; the K/S value rises from 23 to 26.1.

What is claimed is:
 1. A method for the permanent flameproof finishingof cellulose fibers and articles containing cellulose fibers, comprisingtreating said cellulose fibers or said articles containing cellulosefibers under alkaline conditions, during which a swelling of the fibersoccurs, and then treating the swollen fibers so produced with a cyanuricchloride derivative in an aqueous-alkaline phase, wherein a4,6-dichloro-1,3,5-triazine-2-yl amine of formula I or II is used assaid cyanuric chloride derivative:

wherein: R¹ and R² are the same or different and are selected from thegroup consisting of: H; (C₁-C₆) alkyl; benzyl; phenyl; ω-amino (C₂-C₆)alkyl; ω-hydroxy (C₂-C₆) alkyl; —(CH₂)_(m)SO₂—OH or —(CH₂)_(m)—COOH, inwhich m is 1 or 2, as well as their amides; —(CH₂)_(n)—P(O)(OR′)₂ inwhich n=1, 2 or 3 and R′═H, CH₃ or C₂H₅; o-, m- or p-C₆H₄—SO₂NH₂; ando-, m- or p-C₆H₄—N(CH₃)₃⊕; or R¹ and R² together form an ethylene-,trimethylene- or bismethylene imino group; R³ in formula II is selectedfrom the group consisting of: para- or meta-phenylene; 1,4-, 1,3- or2,6-naphthylene; (C₂-C₆) alkylene; —C₂H₄—NH—C₂H₄—;C₂H₄—NH—C₂H₄—NH—C₂H₄—; C₂H₄—O—C₂H₄—; and C₆H₄—NHCONH—C₆H₄—; R⁴ isselected from the group consisting of: H; (C₁- C₃) alkyl; aminoethyl;and aminopropyl; or both R⁴ groups together form ethylene or propylene.2. The method according to claim 1, wherein said4,6-dichloro-1,3,5-triazine-2-yl amine is selected from the groupconsisting of: 2-amino-4,6-dichlorotriazine;2-aminoethylamino-2,4-dichlorotriazine;2-(p-benzenesulfonamide-amino)-4,6-dichlorotriazine; a salt, especiallya halogenide of2-(p-trimethylammonium-benzene-amino)-4,6-dichlorotriazine;bis-N,N′-(4,6-dichloro-triazine-2-yl)-p-phenylene diamine;bis-N,N′-4,6-dichlorotriazine-2-yl)-(C₂ to C₄) alkene diamine; andbis—(4,6-dichlorotriazine-2-yl)-aminoethylphosphonate.
 3. The methodaccording to either claim 1 or 2, characterized in that the cellulosefiber is a cotton or viscose fiber and that it is in the form of aflock, yarn, textile fabric or fleece.
 4. The method according to eitherclaim 1 or claim 2, wherein the 4,6-dichlorotriazinyl amine compound isused in an amount corresponding to 20 to 80% by wt. relative to thecellulose.
 5. The method according to either claim 1 or claim 2,characterized in that at least one 4,6-dichlorotriazinyl amine compoundis used in an amount corresponding to a nitrogen content of at least 2%by wt., relative to the finished cellulose.
 6. The method of claim 5,wherein said at least one 4,6-dichlorotriazinyl amine compound is usedin an amount of 3 to 7% by wt. relative to the fmished cellulose.
 7. Themethod of either claim 1 or claim 2, wherein before, during or after theflameproof finishing with a dichlorotriazinyl amine compound, saidcellulose is additionally finished with a phosphorus-containing compoundand wherein the phosphorus content during the additional finishing is atleast 1% by wt. relative to said cellulose.
 8. The method of claim 7,wherein said phosphorus-containing compound is selected from the groupconsisting of: dialkylphosphonocarboxylic acid amides and theirN-methylol compounds; phosphonates; tetrahydroxymethylphosphonium salts;phosphates; hydrogen phosphates; and phosphorus-containing triazinylamino compounds; and wherein said phosphorous-containing compound bindsto the cellulose either alone or in the presence of urea or of a sourceof formaldehyde.
 9. Cellulose fibers finished in a permanentlyflameproof manner and articles containing these cellulose fibers,characterized by amino-s-triazine compounds bound to glucose units ofthe cellulose via ether bridges and by the structure of formula III orIV:

wherein: R¹ and R² are the same or different and are selected from thegroup consisting of: H; (C₁ to C₆) alkyl; benzyl; phenyl; ω-amino(C₂-C₆) alkyl; ω-hydroxy (C₂-C₆) alkyl; —(CH₂)_(m)SO₂—OH and—(CH₂)_(m)—COOH, in which m is 1 or 2, as well as their amides;—(CH₂)_(n)—P(O)(OR′)₂ with n=1, 2 or 3 and R′═H, CH₃ or C₂H₅; o-, m- orp-C₆H₄—SO₂NH₂; and o-, m- or p-C₆H₄—N(CH₃)₃⊕; or R¹ and R² together anethylene-, trimethylene- or bismethylene imino group; R³ in formula IVis selected from the group consisting of: para- or meta-phenylene; 1,4-,1,3- or 2,6-naphthylene; (C₂-C₆) alkylene; —C₂H₄—NH—C₂H₄—;C₂H₄—NH—C₂H₄—NH—C₂H₄—; C₂H₄—O—C₂H₄—; and C₆H₄—NHCONH—C₆H₄— R⁴ isselected from the group consisting of: H; (C₁-C₃) alkyl; aminoethyl; andaminopropyl; or both R⁴ groups together form ethylene or propylene; R⁵in formulas III and IV is selected from the group consisting of: Cl; OH;Ocell in which cell is an anhydroglucose unit of cellulose; and OR⁶, orNHR⁶ in which R⁶ standing for a dye group; and wherein q is the averagedegree of substitution per glucose unit.
 10. The finished cellulosefibers of claim 9, wherein q is 1-3.
 11. The finished cellulose fibersof claim 9, wherein said cellulose fibers are in an article selectedfrom the group consisting of: yarn; a fleeces; and a sheet.
 12. Thefinished cellulose fibers of claim 9, wherein said finished cellulosefibers have a nitrogen content of at least 1% by wt.
 13. The finishedcellulose fibers of claim 12, wherein said finished cellulose fibershave a nitrogen content of 2 to 7% by wt.
 14. The finished cellulosefibers of any one of claims 9, 12 or 13, wherein said cellulose fibersadditionally contain a bound phosphorus compound.
 15. The finishedcellulose fibers of claim 14, characterized in that said fibers have anitrogen content in the range of 1 to 7% by wt. and a phosphorus contentin the range of 1 to 7% by wt.
 16. The finished cellulose fibers of anyone of claims 9, 12, or 13, characterized in that they have an LOI valueof at least
 22. 17. The finished cellulose fibers of claim 16, whereinsaid LOI value is greater than 25.